CN100374194C - Method and apparatus for preparing inorganic oxidate or metallic nano-particle - Google Patents
Method and apparatus for preparing inorganic oxidate or metallic nano-particle Download PDFInfo
- Publication number
- CN100374194C CN100374194C CNB2006100888174A CN200610088817A CN100374194C CN 100374194 C CN100374194 C CN 100374194C CN B2006100888174 A CNB2006100888174 A CN B2006100888174A CN 200610088817 A CN200610088817 A CN 200610088817A CN 100374194 C CN100374194 C CN 100374194C
- Authority
- CN
- China
- Prior art keywords
- reactor
- hollow
- metal
- measuring pump
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 title claims description 21
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 239000012510 hollow fiber Substances 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 31
- 239000002082 metal nanoparticle Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- 230000001376 precipitating effect Effects 0.000 claims description 22
- 238000003860 storage Methods 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- AJIPIJNNOJSSQC-NYLIRDPKSA-N estetrol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)[C@@H]4O)O)[C@@H]4[C@@H]3CCC2=C1 AJIPIJNNOJSSQC-NYLIRDPKSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0047—Preparation of sols containing a metal oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1893—Membrane reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/04—Specific sealing means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/089—Liquid-solid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
Abstract
The invention relates to a method for preparing inorganic oxide and metal nanometer particle and a relative device, wherein it comprises: with mechanical mixing and ultra-sonic induction, using meter pump (2) to disperse the deposit agent or reducer via hollow fiber film (4) into metal salt solution, or using meter pump 92) to disperse the metal salt solution via hollow fiber film (4) to the deposit agent or reducer, to make the metal ion form nanometer hydroxide or metal nanometer particle colloid; burning said deposit to obtain the nanometer inorganic oxide, and the metal nanometer particle colloid can be used as the predecessor for preparing nanometer catalyst. The inventive product has uniform diameter.
Description
Technical field
The present invention relates to the preparation method and the relevant device of a kind of inorganic oxide nanoparticles or metal nanoparticle, belong to the preparation field of nano material.The inorganic oxide nanoparticles of preparation or metal nanoparticle can be used as the presoma of preparation nanocatalyst or be used for the preparation of other nanometer pulverulent material.
Background technology
The traditional nano-powder material or the preparation method of nanocatalyst have the precipitation method, sol-gal process, hydrothermal synthesis method, Hydrolyze method, complex compound thermal decomposition method, reverse micro emulsion method, metal ion liquid phase reduction, lamina membranacea agent method, physics or chemical vapour deposition technique etc.When preparation nano-powder material or nanocatalyst, the precipitation method, sol-gal process, hydrothermal synthesis method, Hydrolyze method, complex compound thermal decomposition method, metal ion liquid phase reduction exist process conditions and are difficult to control, powder product distribution of particle sizes is wide, and there are the preparation cost height in lamina membranacea agent method, reverse micro emulsion method, physics or chemical vapour deposition technique, are difficult to form large-scale production.
The precipitation method and metal ion liquid phase reduction are respectively the common methods of large-scale production inorganic nanometer powder or metal nanoparticle, for example industrially prepare nano Ce with coprecipitation
1-xZr
xO
2Solid solution.But these two kinds of methods exist precipitating reagent or reductant concentration inhomogeneous in technical process, and crystallization process is difficult to the effectively shortcoming of control.And the nano particle size distribution of preparing is wide and inhomogeneous, makes its physical and chemical performance be difficult to be protected.
Summary of the invention
The preparation method and the relevant device that the purpose of this invention is to provide a kind of inorganic oxide nano-powder or metal nanoparticle (colloidal sol) overcome the shortcoming of the conventional precipitation method or metal ion liquid phase reduction, make precipitation or reduction reaction even, speed-controllable.
The objective of the invention is to utilize barrier diffusion method that precipitating reagent or reducing agent are evenly joined lentamente realizes in the reaction system.
The preparation facilities of a kind of inorganic oxide or metal nanoparticle is characterized in that: complete equipment is made up of agitator 1, measuring pump 2, reactor 3, storage tank 5 and supersonic generator 6;
The ring-type hollow fiber film tube that multilayer links to each other is set in the reactor 3 from top to bottom, and the end that the axle of agitator 1 has paddle 8 extend in the space that this multilayer ring-type hollow fiber film tube is surrounded in the reactor;
When prepared in laboratory inorganic oxide nanoparticles or metal nanoparticle, reactor 3 places in the supersonic generator 6, and hollow-fibre membrane 4 is connected with measuring pump 2 by hollow-fibre membrane pipeline opening 7, and measuring pump 2 is connected with storage tank 5;
When industrial mass production inorganic oxide nanoparticles or metal nanoparticle, reactor 3 is connected with supersonic generator 6, and an end of reactor 3 is provided with reacting product outlet 10, the other end is provided with two solution inlets 9, one of them solution inlet 9 is connected with measuring pump 2, hollow-fibre membrane pipeline opening 7 is positioned near the solution that connects measuring pump 29 places that enter the mouth, and measuring pump 2 is connected with storage tank 5.
Described hollow-fibre membrane 4 can be organic hollow tunica fibrosa or inorganic ceramic hollow-fibre membrane, and the membranous wall aperture is 0.03-0.3 μ m.
A kind of method of utilizing described equipment to realize prepared in laboratory inorganic oxide or metal nanoparticle is characterized in that, comprises the steps:
(1) preparing metal salting liquid, and solution transferred in the reactor 3, precipitating reagent or reducing agent are put into storage tank 5;
(2) start measuring pump 2, precipitating reagent or reducing agent are injected into the pipeline of hollow-fibre membrane 4 through measuring pump 2 and hollow-fibre membrane pipeline opening 7 from storage tank 5, start agitator 1 and supersonic generator 6, precipitating reagent or reducing agent are diffused in the metal salt solution in the reactor 3 by the micropore on hollow-fibre membrane 4 duct walls react;
When product was precipitation, metal salt solution and precipitating reagent reacted in reactor 3 after 2-8 hour, stopped reaction, collected and sediment separate out, obtained inorganic oxide nanoparticles after the calcination;
Product is not when precipitation, when the amount of substance of reducing agent is than the high 5-20 of amount times of metal ion species in the reactor 3, stops reaction, and gained solution is metal nanoparticle colloidal sol.
A kind ofly utilize described equipment to realize that industrial mass production prepares the method for inorganic oxide or metal nanoparticle, it is characterized in that, comprise the steps:
(1) preparing metal salting liquid, and the solution inlet 9 of solution by not being connected with measuring pump 2 transferred in the reactor 3, precipitating reagent or reducing agent are put into storage tank 5;
(2) start measuring pump 2, precipitating reagent or reducing agent are injected into the pipeline of hollow-fibre membrane from the solution inlet 9 and the hollow-fibre membrane pipeline opening 7 of storage tank 5 through measuring pump 2, connection measuring pump 2, start agitator 1 and supersonic generator 6, precipitating reagent or reducing agent are diffused in the metal salt solution in the reactor 3 by the micropore on hollow-fibre membrane 4 duct walls react;
When product is precipitation, after metal salt solution and the precipitating reagent stop 2-8 in reactor 3 hour, flow out, collect and sediment separate out, obtain inorganic oxide nanoparticles after the calcination from reacting product outlet 10;
Product is not when precipitation, when the amount of substance of reducing agents is than the high 5-20 of amount times of metal ion species near the reacting product outlet 10 in the reactor 3, solution is flowed out from reacting product outlet 10, and gained solution is metal nanoparticle colloidal sol.
The preparation method of described a kind of inorganic oxide or metal nanoparticle is characterized in that: the flow of measuring pump 2 is 0.2-100ml/min, and the rotating speed of agitator 1 is 100-200 commentaries on classics/min, and the tranmitting frequency of supersonic generator 6 is 60-120KHz.
The preparation method of described inorganic oxide or metal nanoparticle can also be in step (1) precipitating reagent or reducing agent to be put into reactor 3, and metal salt solution is put into storage tank 5; Corresponding step (2) is diffused into metal salt solution in the precipitating reagent or reductant solution in the reactor 3 by the micropore on hollow-fibre membrane 4 duct walls.
Described metal salt solution is the inorganic salts or the organic slat solution of alkaline-earth metal, rare earth metal, magnesium-yttrium-transition metal.
Described precipitating reagent is NH
4OH, NaOH or oxalic acid.
Described reducing agent is N
2H
4, NaBH
4, ascorbic acid, oxalic acid, formaldehyde or ethanol.
The invention has the beneficial effects as follows:
Utilize method and apparatus of the present invention to prepare inorganic oxide nanoparticles or metal nanoparticle, have that cost is low, reaction evenly, the effective advantage of crystallization control process, the particle size of preparation is little, even particle size distribution is consistent.
Description of drawings
Fig. 1 ultrasonic wave is induced barrier diffusion method prepared in laboratory inorganic oxide nanoparticles or metal nanoparticle apparatus system schematic diagram;
Fig. 2 ultrasonic wave is induced barrier diffusion method industrial mass production inorganic oxide nanoparticles or metal nanoparticle apparatus system schematic diagram;
Reference numeral:
1, agitator, 2, measuring pump, 3 reactors, 4, hollow-fibre membrane, 5, storage tank, 6, supersonic generator, 7, hollow-fibre membrane pipeline opening 8, paddle, 9, the solution inlet, 10, reacting product outlet.
The cut-away view of reactor 3 when Fig. 3 prepared in laboratory inorganic oxide nanoparticles or metal nanoparticle;
The cut-away view of reactor 3 when Fig. 4 industrial mass production inorganic oxide nanoparticles or metal nanoparticle;
Fig. 5 utilizes the Ce of the inventive method preparation
0.6Zr
0.4O
2Solid solution HRSEM photo
The Ce of the conventional precipitation method preparation of Fig. 6
0.6Zr
0.4O
2Solid solution HRSEM photo
Fig. 7 utilizes the Ag nano particle TEM photo of the inventive method preparation
The Ag nano particle TEM photo of the conventional liquid phase reduction preparation of Fig. 8
The specific embodiment
Embodiment 1
With the cerous nitrate (Ce (NO that has weighed
3)
36H
2O) and zirconyl nitrate (ZrONO
4) be dissolved in the 300ml deionized water, this solution is transferred to (1000ml) in the reactor 3, the tranmitting frequency that supersonic generator 6 is set is 60 hertz, bath temperature is 60 ℃, start agitator 1, making its rotating speed is 100 rev/mins, utilizes measuring pump 2 with the fluid flow of 0.2ml/min ammoniacal liquor to be injected in the pipeline of hollow-fibre membrane 4 through hollow-fibre membrane pipeline opening 7, and the micropore of ammoniacal liquor by hollow-fibre membrane 4 is diffused into and contains Ce
3+And Zr
4+In the ion solution, slowly produce light-yellow precipitate, when the pH of solution value reaches 10, close measuring pump 2, supersonic generator 6 and agitator 1, filtering precipitate, sediment 500 ℃ of calcinations 4 hours, promptly gets light yellow Ce 110 ℃ of oven dry 10 hours
0.6Zr
0.4O
2Solid solution.This product specific area is 108m
2/ g, particle size is less than the Ce of 10nm and even particle size distribution unanimity (Fig. 5) and traditional precipitation method preparation
0.6Zr
0.4O
2Solid solution (Fig. 6) is compared, and utilizes the Ce of method preparation of the present invention
0.6Zr
0.4O
2It is little that solid solution has granularity, advantages such as narrow particle size distribution.Utilize H
2-O
2This nano Ce that impulse method is measured
0.6Zr
0.4O
2The solid solution oxygen storage capacity is 0.757mmol/g, than the Ce of traditional precipitation method preparation
0.6Zr
0.4O
2Solid solution oxygen storage capacity (0.357mmol/g) exceeds one times.
With the silver nitrate (AgNO that has weighed
3) and polyvinylpyrrolidone (PVP, molecular weight are 40000) be dissolved in the 300ml deionized water, this solution is transferred to (1000ml) in the tank reactor 3, with the sodium borohydride (NaBH that has weighed
4) be dissolved in the 30ml deionized water, this solution to be transferred in the storage tank in 5, the tranmitting frequency that supersonic generator 6 is set is 120 hertz, bath temperature is 60 ℃, start agitator 1, making its rotating speed is 200 rev/mins, utilize measuring pump 2 with the fluid flow of 1.2ml/min with sodium borohydride (NaBH
4) aqueous solution is injected in the pipeline of hollow-fibre membrane 4 sodium borohydride (NaBH through hollow-fibre membrane pipeline opening 7
4) micropore of the aqueous solution by hollow-fibre membrane 4 be diffused into and contain Ag
+In the ion solution, solution colour slowly becomes brown from water white transparency, as sodium borohydride (NaBH
4) aqueous solution all is injected in the tank reactor, closes measuring pump 2, supersonic generator 6 and agitator 1, promptly gets brown Ag colloidal sol.The Ag particle size is 5-8nm and even particle size distribution unanimity (Fig. 7) and traditional metal ion liquid phase NaBH
4The Ag nano particle (Fig. 8) of reducing process preparation is compared, and it is little that the Ag nano particle that utilizes method of the present invention to prepare has granularity, advantages such as narrow particle size distribution.
Claims (8)
1. the preparation equipment of inorganic oxide or metal nanoparticle, it is characterized in that: complete equipment is made up of agitator (1), measuring pump (2), reactor (3), storage tank (5) and supersonic generator (6);
The ring-type hollow fiber film tube that multilayer links to each other is set in the reactor (3) from top to bottom, and the end that the axle of agitator (1) has paddle (8) extend in the space that this multilayer ring-type hollow fiber film tube is surrounded in the reactor;
When prepared in laboratory inorganic oxide nanoparticles or metal nanoparticle, reactor (3) places in the supersonic generator (6), hollow-fibre membrane (4) is connected with measuring pump (2) by hollow-fibre membrane pipeline opening (7), and measuring pump (2) is connected with storage tank (5);
When industrial mass production inorganic oxide nanoparticles or metal nanoparticle, reactor (3) is connected with supersonic generator (6), and an end of reactor (3) is provided with reacting product outlet (10), the other end is provided with two solution inlets (9), one of them solution inlet (9) is connected with measuring pump (2), hollow-fibre membrane pipeline opening (7) is positioned near the solution inlet (9) that connects measuring pump (2) to be located, and measuring pump (2) is connected with storage tank (5).
2. the preparation equipment of a kind of inorganic oxide according to claim 1 or metal nanoparticle is characterized in that: hollow-fibre membrane (4) is organic hollow tunica fibrosa or inorganic ceramic hollow-fibre membrane, and the membranous wall aperture is 0.03 μ m-0.3 μ m.
3. a method of utilizing the described equipment of claim 1 to realize prepared in laboratory inorganic oxide or metal nanoparticle is characterized in that, comprises the steps:
1) preparing metal salting liquid, and solution transferred in the reactor (3), precipitating reagent or reducing agent are put into storage tank (5);
2) start measuring pump (2), precipitating reagent or reducing agent are injected into the pipeline of hollow-fibre membrane (4) through measuring pump (2) and hollow-fibre membrane pipeline opening (7) from storage tank (5), start agitator (1) and supersonic generator (6), precipitating reagent or reducing agent are diffused in the metal salt solution in the reactor (3) by the micropore on hollow-fibre membrane (4) duct wall react;
When product was precipitation, metal salt solution and precipitating reagent reacted in reactor (3) after 2-8 hour, stopped reaction, collected and sediment separate out, obtained inorganic oxide nanoparticles after the calcination;
Product is not when precipitation, when the amount of substance of reducing agent is than the high 5-20 of amount times of metal ion species in the reactor (3), stops reaction, and gained solution is metal nanoparticle colloidal sol.
4. one kind is utilized the described equipment of claim 1 to realize that industrial mass production prepares the method for inorganic oxide or metal nanoparticle, it is characterized in that, comprises the steps:
1) preparing metal salting liquid, and the solution inlet (9) of solution by not being connected with measuring pump (2) transferred in the reactor (3), precipitating reagent or reducing agent are put into storage tank (5);
2) start measuring pump (2), precipitating reagent or reducing agent are injected into the pipeline of hollow-fibre membrane from the solution inlet (9) and the hollow-fibre membrane pipeline opening (7) of storage tank (5) through measuring pump (2), connection measuring pump (2), start agitator (1) and supersonic generator (6), precipitating reagent or reducing agent are diffused in the metal salt solution in the reactor (3) by the micropore on hollow-fibre membrane (4) duct wall react;
When product is precipitation, after metal salt solution and the precipitating reagent stop 2-8 in reactor (3) hour, flow out, collect and sediment separate out, obtain inorganic oxide nanoparticles after the calcination from reacting product outlet (10);
Product is not when precipitation, when the amount of substance of reducing agent is than the high 5-20 of amount times of metal ion species near the reacting product outlet (10) in the reactor (3), solution is flowed out from reacting product outlet (10), and gained solution is metal nanoparticle colloidal sol.
5. according to the preparation method of claim 3 or 4 described a kind of inorganic oxides or metal nanoparticle, it is characterized in that: the flow of measuring pump (2) is 0.2-100ml/min, the rotating speed of agitator (1) is 100-200 commentaries on classics/min, and the tranmitting frequency of supersonic generator (6) is 60-120KHz.
6. according to the preparation method of claim 3 or 4 described a kind of inorganic oxides or metal nanoparticle, it is characterized in that: metal salt solution is the inorganic salts or the organic slat solution of alkaline-earth metal, rare earth metal, magnesium-yttrium-transition metal.
7. according to the preparation method of claim 3 or 4 described a kind of inorganic oxides or metal nanoparticle, it is characterized in that: precipitating reagent is NH
4OH, NaOH or oxalic acid.
8. according to the preparation method of claim 3 or 4 described a kind of inorganic oxides or metal nanoparticle, it is characterized in that: reducing agent is N
2H
4, NaBH
4, ascorbic acid, oxalic acid, formaldehyde or ethanol.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100888174A CN100374194C (en) | 2006-07-19 | 2006-07-19 | Method and apparatus for preparing inorganic oxidate or metallic nano-particle |
| US11/777,090 US8133441B2 (en) | 2006-07-19 | 2007-07-12 | Apparatus and process for metal oxides and metal nanoparticles synthesis |
| US13/176,728 US8382877B2 (en) | 2006-07-19 | 2011-07-05 | Process for metal oxide and metal nanoparticles synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100888174A CN100374194C (en) | 2006-07-19 | 2006-07-19 | Method and apparatus for preparing inorganic oxidate or metallic nano-particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1907556A CN1907556A (en) | 2007-02-07 |
| CN100374194C true CN100374194C (en) | 2008-03-12 |
Family
ID=37698886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100888174A Expired - Fee Related CN100374194C (en) | 2006-07-19 | 2006-07-19 | Method and apparatus for preparing inorganic oxidate or metallic nano-particle |
Country Status (2)
| Country | Link |
|---|---|
| US (2) | US8133441B2 (en) |
| CN (1) | CN100374194C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161342B (en) * | 2007-11-23 | 2010-06-23 | 北京工业大学 | Method for preparing high activity loading type RhxAu-x/Y nanometer catalyst |
| CN101532168B (en) * | 2009-03-06 | 2011-08-03 | 宁波大学 | Complex crystal cultivation device capable of inhibiting growth of crystal with multi-crystallization water |
| CN101532167B (en) * | 2009-03-06 | 2011-08-03 | 宁波大学 | Complex crystal synthesis device having retardance function for easy-weathered crystal growth |
| US20130216646A1 (en) * | 2011-04-11 | 2013-08-22 | Kandalam V. Ramanujachary | Nanoparticles of Nutritional and Pharmaceutical Compounds |
| US20130087020A1 (en) * | 2011-10-07 | 2013-04-11 | University Of Southern California | Continuous flow synthesis of nanomaterials using ionic liquids in microfluidic reactors |
| CN102689017A (en) * | 2012-05-25 | 2012-09-26 | 南京白云化工环境监测有限公司 | Automatic production equipment for manufacturing copper nickel nano-alloy |
| US9624598B2 (en) * | 2012-09-06 | 2017-04-18 | The Research Foundation For The State University Of New York | Segmented metallic nanostructures, homogeneous metallic nanostructures and methods for producing same |
| CA2969317C (en) * | 2014-12-24 | 2023-06-13 | Dic Corporation | Hollow-fiber degassing module and inkjet printer |
| CN104934330A (en) * | 2015-05-08 | 2015-09-23 | 京东方科技集团股份有限公司 | Film transistor and preparation method thereof, array substrate and display panel |
| JP6823831B2 (en) | 2015-07-23 | 2021-02-03 | 昭栄化学工業株式会社 | Nanocrystal manufacturing method and nanocrystal manufacturing equipment |
| CN106270554B (en) * | 2016-09-28 | 2018-04-13 | 广州凯耀资产管理有限公司 | A kind of preparation method of super-fine cobalt powder |
| US10961665B2 (en) * | 2017-10-31 | 2021-03-30 | Koppers Delaware, Inc. | Rail joint assembly having forged rail joint bars |
| CN114197088B (en) * | 2021-11-09 | 2023-04-21 | 华南理工大学 | Method for preparing nanofiber or nanoparticle by ultrasonic induction and film formed by nanomaterial |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
| US6558575B2 (en) * | 2001-02-07 | 2003-05-06 | Agfa-Gevaert | Perparation of improved ZnS:Mn phosphors |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2940831A (en) * | 1954-12-23 | 1960-06-14 | Nossardi Gerolamo | Method of and installation for the continuous extraction of magnesium with milk of lime from sea waters and the like |
| JP3011530B2 (en) * | 1992-04-06 | 2000-02-21 | 森永乳業株式会社 | Spreads and how to make them |
| GB9606738D0 (en) * | 1996-03-29 | 1996-06-05 | Disperse Tech Ltd | Dispersion of immiscible phases |
| EP1125121B1 (en) * | 1998-10-28 | 2007-12-12 | Covaris, Inc. | Apparatus and methods for controlling sonic treatment |
| US6209855B1 (en) * | 1999-05-10 | 2001-04-03 | Canzone Limited | Gas/liquid mixing apparatus and method |
| JP2001239140A (en) * | 1999-12-22 | 2001-09-04 | Reika Kogyo Kk | Device for reaction and agitation, device for reaction, fractionation and filtration, and method for fractionation, method for preparation and method for filtration |
| AU2001252588A1 (en) * | 2000-04-28 | 2001-11-12 | Tanabe Seiyaku Co., Ltd. | Method for preparing microsphere |
| EP1412418A1 (en) * | 2001-08-03 | 2004-04-28 | Akzo Nobel N.V. | Process to make dispersions |
| WO2003035308A1 (en) * | 2001-10-26 | 2003-05-01 | Miyazaki Prefecture | Monodisperse metal spherical particle and production method thereof |
| CN101229098B (en) * | 2002-09-11 | 2012-02-29 | 田边三菱制药株式会社 | Method for preparation of microsphere and apparatus therefor |
| CN1688381A (en) * | 2002-10-02 | 2005-10-26 | 荷兰联合利华有限公司 | Method for controlling droplet size of an emulsion when mixing two immiscible fluids |
| WO2004071638A2 (en) * | 2003-02-11 | 2004-08-26 | Regents Of The University Of California, The | Microfluidic devices and method for controlled viscous shearing and formation of amphiphilic vesicles |
| CA2543969A1 (en) * | 2003-10-31 | 2005-05-12 | Chevron Phillips Chemical Company Lp | Method and system to add high shear to improve an ionic liquid catalyzed chemical reaction |
| US7053021B1 (en) * | 2004-04-22 | 2006-05-30 | The Research Foundation Of The State University Of New York | Core-shell synthesis of carbon-supported alloy nanoparticle catalysts |
| WO2006006349A1 (en) * | 2004-07-07 | 2006-01-19 | Kaneka Corporation | Process for producing polymer-modified nanoparticle |
| KR100753773B1 (en) * | 2005-08-04 | 2007-08-30 | 학교법인 포항공과대학교 | Method for preparing perovskite oxide nanopowders |
-
2006
- 2006-07-19 CN CNB2006100888174A patent/CN100374194C/en not_active Expired - Fee Related
-
2007
- 2007-07-12 US US11/777,090 patent/US8133441B2/en not_active Expired - Fee Related
-
2011
- 2011-07-05 US US13/176,728 patent/US8382877B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
| US6558575B2 (en) * | 2001-02-07 | 2003-05-06 | Agfa-Gevaert | Perparation of improved ZnS:Mn phosphors |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110286904A1 (en) | 2011-11-24 |
| US8382877B2 (en) | 2013-02-26 |
| US8133441B2 (en) | 2012-03-13 |
| US20100025224A1 (en) | 2010-02-04 |
| CN1907556A (en) | 2007-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100374194C (en) | Method and apparatus for preparing inorganic oxidate or metallic nano-particle | |
| Bao et al. | Compositions, structures, and catalytic activities of CeO2@ Cu2O nanocomposites prepared by the template-assisted method | |
| Chen et al. | Fabricate globular flower-like CuS/CdIn2S4/ZnIn2S4 with high visible light response via microwave-assisted one–step method and its multipathway photoelectron migration properties for hydrogen evolution and pollutant degradation | |
| CN101947448B (en) | Nano-gold catalyst supported on combined metal oxide, preparation method and application thereof | |
| CN104080728B (en) | Metal oxide nanorods array in monolith substrate | |
| CN102139197B (en) | Method for preparing modified micro granules | |
| CN104209529B (en) | A kind of method of continuous production super fine silver powder based on microchannel hybrid reaction system | |
| Wang et al. | Self-organization of layered inorganic membranes in microfluidic devices | |
| CN102019431A (en) | Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof | |
| CN106270543B (en) | The method for continuously preparing the controllable Triangular nanoplates of arrangement mode | |
| CN103263915A (en) | Hydrotalcite-loaded nanometer platinum catalyst as well as preparation method and application thereof | |
| CN107617750B (en) | The method for preparing Ag/ redox graphene composite nano materials | |
| Zhu et al. | In situ dissolution–diffusion toward homogeneous multiphase Ag/Ag2S@ ZnS core–shell heterostructures for enhanced photocatalytic performance | |
| CN102744421A (en) | Method for preparing large-scale Ag nanowires in aqueous solution | |
| Han et al. | One-pot synthesis of a Au@ TiO 2 core–shell nanocomposite and its catalytic property | |
| CN104841437A (en) | Method for preparing copper-zinc catalyst by using micro-channel reactor | |
| CN109718775A (en) | A kind of CuCo2O4The preparation method of nano spinel catalyst | |
| CN102553586B (en) | Cerium-containing composite metal oxide loaded nano-gold and preparation method and application thereof | |
| Valente et al. | A simple environmentally friendly method to prepare versatile hydrotalcite-like compounds | |
| Ozerova et al. | Magnetically recovered Co and Co@ Pt catalysts prepared by galvanic replacement on aluminum powder for hydrolysis of sodium borohydride | |
| Zardi et al. | Mild microfluidic approaches to Oxide nanoparticles synthesis | |
| CN106824234B (en) | The method for preparing sea urchin shape Ag/AgCl/ZnO nanocomposite | |
| Luo et al. | Continuous synthesis of reduced graphene oxide-supported bimetallic NPs in liquid–liquid segmented flow | |
| CN105522162A (en) | Method for preparing silver nanoparticles by step-by-step growth method | |
| CN105170050B (en) | Preparation method of LaNiO3 ball with micro-nano structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080312 |